CN1304097C - Gemini type fluorocarbon surfactant and preparation method thereof - Google Patents
Gemini type fluorocarbon surfactant and preparation method thereof Download PDFInfo
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- CN1304097C CN1304097C CNB2005100410666A CN200510041066A CN1304097C CN 1304097 C CN1304097 C CN 1304097C CN B2005100410666 A CNB2005100410666 A CN B2005100410666A CN 200510041066 A CN200510041066 A CN 200510041066A CN 1304097 C CN1304097 C CN 1304097C
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- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000004094 surface-active agent Substances 0.000 title abstract description 30
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title abstract description 13
- -1 perfluoroalkyl sulfonamide Chemical class 0.000 claims abstract description 26
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 11
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 8
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005187 foaming Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 125000006850 spacer group Chemical group 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 125000005647 linker group Chemical group 0.000 abstract 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 abstract 1
- 239000001294 propane Substances 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YVWGMAFXEJHFRO-UHFFFAOYSA-N halopropane Chemical compound FC(F)C(F)(F)CBr YVWGMAFXEJHFRO-UHFFFAOYSA-N 0.000 description 1
- 229950000188 halopropane Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a novel Gemini type fluorocarbon surfactant, which is a novel Gemini type fluorocarbon surfactant with hydrophilic flexible spacer group and taking hydrophilic monoester dichloropropane as a linking group, and has the chemical name of N, N, N ', N ' -tetramethyl-N, N ' -bis [ (perfluoroalkyl sulfonamide) -alkyl ] -2-monoester-propane diammonium. The surfactant is prepared by reacting perfluoroalkyl sulfonyl fluoride with N, N-dimethyl-1, 2-ethylenediamine or N, N-dimethyl-1, 3-propanediamine to obtain an intermediate product N- [ (dimethylamino) -alkyl ] perfluoroalkyl sulfonamide, and then performing quaternization reaction with monoester dichloropropane. The surfactant can greatly reduce the surface tension of a solution, has strong foaming power, excellent detergency, no peculiar smell, good color and luster, good compounding performance and simple synthesis process, and is expected to be popularized and used.
Description
Technical field
The present invention relates to a kind of surfactant and preparation method thereof, particularly fluorine-carbon sufactant and preparation method thereof.
Background technology
Fluorine surfactant is because of the hydrogen partial in the hydrocarbon chain hydrophobic grouping or all replaced by fluorine atom, thereby has high surface-active.Fluorine surfactant has " three height and two are hated " (high surface, high thermal stability, high chemical stability; Hydrophobic, increase oil) special performance, its high surface and hydrophobic and lyophobic property can reduce the surface tension of water and organic solvent effectively, and high thermal stability and high chemical stability can make it use under high temperature, strong acid and strong base and the condition that has oxide to exist, these performances be hc-surfactant can't be obtained.Yet the superpower hydrophobic and oil repellent performance of fluorocarbon chain makes its solubility in water and some organic solvent very low, and this has limited its application extension to a certain extent.
The double type surfactant is the surfactant that a class has a class special construction of two hydrophilic radicals and two lipophilic groups, compare with the conventional surfactants of same carbon atoms number, capillary critical micelle concentration (CMC) can reduce by 2～3 orders of magnitude, is called surfactant of new generation by people.Document announcement is arranged, synthesized 100 surplus kind of double type surfactant, great majority no industrial values, be not that process route is long, be exactly raw material costliness, synthesis condition harshness etc., real industrialized product only has only several.The double type surfactant of having reported at present is in the majority with anionic, cation, and amphoteric gemini type surfactant report is very few, still is in the research and development stage.
Summary of the invention
The object of the present invention is to provide a kind of novel gemini type fluorocarbon surfactant, this surfactant can have the advantage of hydrocarbon class double type surfactant and common fluorocarbon surfactant simultaneously, and can overcome the two shortcoming, have higher surface-active, lower CMC value.
Another object of the present invention is to provide a kind of preparation method of novel gemini type fluorocarbon surfactant, this method is simple to operate, and the reaction condition gentleness is easy to control, and equipment is not had harsh requirement.
Fluorine-carbon sufactant chemistry of the present invention is by name:
N, N, N ', N '-tetramethyl-N, N '-two [(perfluoroalkyl sulfoamido)-alkyl]-2-monoesters base-propane-diammonium is called for short NGFEA,
Have following structural formula:
N=2 or 3, m=4～12,
R=-O (PO
2)
-2,-O (SO
3)
-,-(SO
3)
-Or-COO
-
Surfactant of the present invention is a light yellow solid, belongs to betaine type amphoteric surfactant, and dissolubility is better in alcohol.It is a spacer group with hydrophilic monoesters dichloropropane, can greatly reduce the surface tension of solution, and foaming power is strong, the good and free from extraneous odour of detergency, and color and luster is good, and compound property is good.
Fluorine-carbon sufactant of the present invention makes carbon fluorine chain have stronger hydrophobicity because of the high electronegativity of fluorine atom, and attractive interaction is lower between the carbon fluorine chain self.A little less than the active force between fluorocarbon chain, hydrophobicity is strong, and the effect of repelling water is stronger, and therefore easier in solution surface absorption with form micelle in water, it not only has very low surface tension, and very low critical micelle concentration is arranged.This novel gemini type fluorocarbon surfactant has been obtained breakthrough on molecular structure simultaneously, two ion head bases connect by chemical bond by spacer group, caused two surfactant monomer ions to connect quite closely thus, cause and more be easy to generate strong interaction between its carbochain, both strengthened the hydrophobic adhesion between hydrocarbon chain, and the repulsion between ion head base tendency is limited by chemical bonding force and is weakened greatly, have two long hydrophobic chains in its molecular structure, the hydrone degreeof tortuosity is strengthened, thereby the raising of the surface-active of the aqueous solution, the CMC value also descends thereupon.
This fluorine-carbon sufactant is by monoesters two halopropanes that contain following structural formula (2) and contain the N-[(dimethylamino of following structural formula (3))-alkyl] the perfluoroalkyl sulfuryl amine reaction makes:
R=-O (PO
2)
2-,-O (SO
3)
-,-(SO
3)
-Or-COO
-,
R
1=Cl or Br,
N=2 or 3, m=4～12;
Reaction equation is as follows:
Above-claimed cpd (3) can be by perfluoroalkyl sulfonyl fluoride that contains following structural formula (4) and the N that contains following structural formula (5), N-dimethyl-1, and 2-ethylenediamine/N, N-dimethyl-1, the reaction of 3-propane diamine makes,
m＝4～12，
NH
2(CH
2)
nN(CH
3)
2 (5)
N=2 or 3;
Reaction equation is as follows:
As seen, this double type surfactant mainly utilizes the quaterisation of tertiary amine and alkyl halide synthetic, and synthetic method is carried out as follows:
1. prepare intermediate product N-[(dimethylamino)-alkyl] the perfluoroalkyl sulfonamide:
Perfluoroalkyl sulfonyl fluoride is that solvent is made solution with the isopropyl ether; The N of equimolar amounts, N-dimethyl-1,2-ethylenediamine or N, N-dimethyl-1,3-propane diamine are that solvent is made solution with the isopropyl ether; Stir down the latter solution is added drop-wise in the former solution, reflux then to be stirred to react and finish, reaction gained mixture is successively after water, aqueous hydrochloric acid solution, the saturated common salt water washing, use anhydrous magnesium sulfate drying, decompression distillation desolventizes then, obtain intermediate product N-[(dimethylamino)-alkyl] perfluoroalkyl sulfonamide, i.e. compound (3).
2. prepare end product fluorine-carbon sufactant (NGFEA):
With intermediate product N-[(dimethylamino)-alkyl] the perfluoroalkyl sulfonamide is dissolved in and makes solution in the anhydrous ethanol solvent, the NaOH that adds the twice mole, after stirring fully in the cold bath, the hot bath heating down, the monoesters two halopropane ethanolic solutions of 1/2nd moles are slowly splashed in this material, add back successive reaction a few hours to finish to reaction, ethanol is removed in distillation, obtaining yellow solid product is fluorine-carbon sufactant, i.e. compound (1).
This reacts raw materials used perfluoroalkyl sulfonyl fluoride, and is homemade, and chemical pure is commercially available; N, N-dimethyl-1, the 2-ethylenediamine, homemade, chemical pure, commercially available; N, N-dimethyl-1, the 3-propane diamine, homemade, chemical pure, commercially available; Other, homemade, chemical pure, commercially available.
The specific embodiment
The invention provides following example, so that describe the preparation of novel gemini type fluorocarbon surfactant in detail.
Embodiment 1:
Taking by weighing 15.06g (0.03mol) full-fluorine octyl sulfuryl fluoride is dissolved in the 50mL isopropyl ether and makes solution, N with 15.06g (0.03mol), N-dimethyl-1, the 3-propane diamine is dissolved in the 25mL isopropyl ether and makes solution, (about 20 ℃) slowly are added drop-wise to the latter solution in the former solution at low temperatures, and constant temperature stirs, the about 0.5h of this dropping process, dropwise, reactant is warming up to 50 ℃, backflow stirring reaction 3h, and the hydrogen fluoride gas that reaction generates absorbs with sodium hydroxide solution, reaction finishes, cooling.After the cooling reactant mixture is washed successively, 0.5% aqueous hydrochloric acid solution is washed, saturated common salt washing and anhydrous magnesium sulfate drying.After desolvating, decompression distillation obtains faint yellow solid product N-[(dimethylamino)-alkyl] perfluorinated octyl sulfuryl amine.
Take by weighing N-[3-(dimethylamino)-propyl group of 17.52g (0.03mol)] perfluorinated octyl sulfuryl amine, join and have rotor, thermometer, in the 250ml four-hole boiling flask of condensing unit, with the 50ml absolute ethyl alcohol is quaternized solvent, the NaOH that adds 2.40g (0.06mol), start magnetic stirring apparatus and connect condensed water, stirring reaction 30min, water bath with thermostatic control is heated to 80 ℃, slowly splash into phosphoric acid lactone dichloropropane 15.675g (being 0.015mol) with dropping funel, weight concentration is 20% phosphoric acid lactone dichloropropane ethanolic solution, in 1h, dropwise, keep 80 ℃ of successive reaction 5h.After reaction was finished, ethanol was removed in distillation, obtains yellow solid product novel gemini type fluorocarbon surfactant: N, N, N ', N '-tetramethyl-N, N '-two [3-(perfluorinated octyl sulfuryl amine base)-propyl group]-2-mono phosphoric acid ester ester group-propane-diammonium.
Embodiment 2
Intermediate product N-[(dimethylamino)-and alkyl] preparation of perfluorinated octyl sulfuryl amine is the same.
Take by weighing N-[3-(dimethylamino)-propyl group of 23.36g (0.04mol)] perfluorinated octyl sulfuryl amine, join and have rotor, thermometer, in the 250ml four-hole boiling flask of condensing unit, with the 70ml absolute ethyl alcohol is quaternized solvent, the NaOH that adds 3.20g (0.08mol), start magnetic stirring apparatus and connect condensed water, stirring reaction 30min, water bath with thermostatic control is heated to 80 ℃, contain sultones dichloropropane 16.10g (being 0.02mol) in slowly splashing into dropping funel, weight concentration is 20% sultones dichloropropane ethanolic solution, in 1h, dropwise, keep 80 ℃ of successive reaction 6h.After reaction was finished, ethanol was removed in distillation, obtains yellow solid product novel gemini type fluorocarbon surfactant NGFPA:N, N, N ', N '-tetramethyl-N, N '-two [3-(perfluorinated octyl sulfuryl amine base)-propyl group]-2-sultones base-propane-diammonium.
Embodiment 3
Intermediate product N-[(dimethylamino)-and alkyl] preparation of perfluorinated octyl sulfuryl amine is the same.
Take by weighing N-[3-(dimethylamino)-propyl group of 23.36g (0.04mol)] perfluorinated octyl sulfuryl amine, join and have rotor, thermometer, in the 250ml four-hole boiling flask of condensing unit, with the 50ml absolute ethyl alcohol is quaternized solvent, the NaOH that adds 3.20g (0.08mol), start magnetic stirring apparatus and connect condensed water, stirring reaction 30min, water bath with thermostatic control is heated to 80 ℃, slowly splash into sulfur acid lactone dichloropropane 17.70g (being 0.015mol) with dropping funel, weight concentration is 20% sultones dichloropropane ethanolic solution, in 1h, dropwise, keep 80 ℃ of successive reaction 8h.After reaction was finished, ethanol was removed in distillation, obtains yellow solid product novel gemini type fluorocarbon surfactant: N, N, N ', N '-tetramethyl-N, N '-two [3-(perfluorinated octyl sulfuryl amine base)-propyl group]-2-sultones base-propane-diammonium.
Embodiment 4
To the fluorine-carbon sufactant N for preparing in the EXAMPLE l, N, N ', N '-tetramethyl-N, N '-two [3-(perfluorinated octyl sulfuryl amine base)-propyl group]-2-mono phosphoric acid ester ester group-propane-diammonium carries out the test of surface-active and foaming properties.Test result is as follows:
In the time of 25 ℃, the aqueous solution lowest surface tension of this surfactant is that 23.2mN/m, critical micelle concentration (CMC) are 1.55 * 10
-3Mol/L, isoelectric point are pH3.0～11.0.
Foaming properties (25 ℃): (mm) (mm) 25 after 27,5 minutes at that time, stability 0.93.
Claims (2)
1, a kind of fluorine-carbon sufactant is characterized in that chemistry is by name:
N, N, N ', N '-tetramethyl-N, N '-two [(perfluoroalkyl sulfoamido)-alkyl]-2-monoesters base-propane-diammonium has following chemical structural formula:
Wherein: n=2 or 3, m=4～12,
R=-O (PO
2)
2-,-O (SO
3)
-,-(SO
3)
-Or-COO
-
The fluorine-carbon sufactant of a claim 1 Preparation Method, it is characterized in that according to the following steps:
1.. intermediate product N-[(dimethylamino)-alkyl] perfluoroalkyl sulfonamide synthetic:
With perfluoroalkyl sulfonyl fluoride is that solvent is made solution with the isopropyl ether, the N of equimolar amounts, and N-dimethyl-1,2-ethylenediamine or N, N-dimethyl-1,3-propane diamine are that solvent is made solution with the isopropyl ether; Stir down the latter solution is added drop-wise in the former solution, reflux then to be stirred to react and finish, reaction gained mixture washes with water successively, aqueous hydrochloric acid solution is washed, saturated common salt washing back anhydrous magnesium sulfate drying, decompression distillation desolventizes then, obtains intermediate product N-[(dimethylamino)-alkyl] the perfluoroalkyl sulfonamide;
2.. synthesizing of finished product fluorine-carbon sufactant:
With intermediate product N-[(dimethylamino)-alkyl] the perfluoroalkyl sulfonamide is dissolved in and makes solution in the absolute ethyl alcohol, add the NaOH that doubles the intermediate product mole, after stirring fully in the cold bath, the hot bath heating down, the ethanolic solution of monoesters two halopropanes of 1/2nd moles is added dropwise in this material, after reaction was finished, ethanol was removed in distillation, obtains the product fluorine-carbon sufactant.
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| CNB2005100410666A CN1304097C (en) | 2005-07-18 | 2005-07-18 | Gemini type fluorocarbon surfactant and preparation method thereof |
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| CN1304097C true CN1304097C (en) | 2007-03-14 |
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| CN1431037A (en) * | 2003-01-24 | 2003-07-23 | 中国科学院上海有机化学研究所 | 3 oxide heteroperfluoro-nonyl fluorocarbon surfactant, its systhesizing method and usages |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402851B (en) * | 2008-10-28 | 2011-01-26 | 大庆油田有限责任公司 | Ternary composite block-resistant protection solution for drive injection well |
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| CN1743062A (en) | 2006-03-08 |
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